WO2010062732A1

WO2010062732A1 - Self-sealing substrate display and color changing apparatus and applications

Info

Publication number: WO2010062732A1
Application number: PCT/US2009/063041
Authority: WO
Inventors: Alain Briancon; Henrik Lindstrom; Martin Moeller; Gavin Copeland; Michael Ryan
Original assignee: Ntera Inc.; Ntera Limited
Priority date: 2008-11-03
Filing date: 2009-11-03
Publication date: 2010-06-03

Abstract

A display made with a self-sealing electrolyte and a method to manufacture the display. The display has a first side and a second side wherein the first side and second side are substantially parallel The display includes: a single substrate, a self-sealing electrolyte layer, a coloring electrode, a second electrode and an insulator layer. The single substrate forms the first side of the display with the self-sealing electrolyte layer forming the second side of the display. The insulator layer is positioned between the coloring electrode and the second electrode and the coloring electrode, second electrode and insulator layer are positioned between the first and second aides of the display The self-sealing electrolyte contains a polymer and electrolyte and at least some portion of electrolyte from the self-sealing electrolyte layer permeates throughout the layers of the display. The display may include a self assembling layer formed from micron sized and nanometer sized particles to form an electrically conductive layer and/or a conductive plus capacitive layer.

Description

SELF-SEAUNG SINGLE SUBSTRATE DISPLAY AND COLOR CHANGING APPARATUS

AND APPLICATIONS FIELD OF INVENTION The present invention generally relates to electrochromic devices. More particularly, the present invention relates to a monolithic architecture for an electrochromic device and electrolytes used with the device that only requires a single substrate for its fabrication, does not require the introduction on sealant on the device, and reduces the number of printing steps.

BACKGROUND Electrochromic materials (often referred to as Chromogens) exhibit reversible or irreversible color change when the compounds gain or lose electrons, or react to protons. Electrochromic devices that exploit the inherent properties of electrochromic compounds find application in large area static displays and automatically dimming mirrors, and are well known.

Electrochromic display/color changing devices create images by patterning the chromogens in specific areas and then selectively modulating across the display. A color- changing device will have a variety of properties depending on the electrochromic material used for the structure. The electro-optical effects can be bistable (where an image is retained on the display until forced to disappear), self-erasing (where an image disappears shortly after the application of charge), or permanent (where an image appears and last forever after the application of a charge). The electro-optic effects of these electrochromic displays may be based on reduction effect (where electrons are being provided to a chromophore structure) or oxidation effect (where electrons are being removed from the chromophore structure) such as those displays disclosed in U.S. Patent Nos. 4,215,917 5,209,871, 6,301,038 and 6,870,657, each of which are incorporated herein by reference in their entirety as if fully set forth. Electro-optic effects can also be created by change in pH level through halochrormcs effect where protons are being generated or removed as disclosed in U.S. Patent Nos. 6,879,424 and 7,054,050. Display /color change effect can also take place through ionochromic effect

A multitude of controlled chromic patterns may individually function as pixels to collectively create a high-resolution image. Typically, these display devices contain a reflective layer underneath the electrochromic compound, respective to the viewer, for reflecting light allowed to pass beyond the electrochromic region. Simply put, the electrochromic segment (whether a icon, image, or part of segmented structure such as digit or tetter) acts as a shutter either blocking light or allowing light to pass through to the underlying reflective layer.

Thin displays are becoming popular for use in many applications due to their low weight, high contrast ratio, and ability to be integrated in new form factors. To achieve this, it is preferable to create displays that only require a single substrate. Unlike LCD systems (Nematic, Twisted Nematic, Cholesteric) that rely on a critical gap for operation, technology such as electrochromism can rely on a single substrate, having the different layers required printed as a single monolithic stack. Recent advancements in electrochromic designs have brought up so called monolith designs where a single substrate is used to provide structural integrity or shape to the display. For such designs, the electrolyte is kept in by toping the display with a top cover. This top cover fulfills the dual functionality of providing an oxygen barrier, water barrier, as well as mechanical protection. A traditional electrochromic structure (often referred to as monolith architecture as in U.S. Patents No. 7,403,319 and 7,460,289 is based on an electrochromic display structure 100 as illustrated in Figure I. This electrochromic display structure 100 is viewed from the top of the display through the top substrate 101. This substrate 103 includes flexible material such as PET, PETG, PEN, thin glass, bendable glass, or any other transparent material. On this substrate 101, a transparent conductor material (metal, organic, semiconductor) layer 102 is deposited on part of the inside of the display. The deposition may be performed using a multiple of means such as printing, sputtering, ion beam deposition. On the bottom interface of layer 102, a layer 103 of electrochromic material is deposited. The layer 103 can be patterned or unpattemed. The areaφ) of electrochromic material function as one or more electrodes ("SEG") or generally associated with the anodic side. The area for such an electrode corresponds to active color area of the color changing structure. An insulation layer 104 is placed next to layer 103 covering its entire area to insulate the SEG electrodes from the charge reservoir layer 105 ("COM") or generally associated with the cathodic side. Layer 104 is an ion conductive insulating layer. The area of Ae charge reservoir layer 105 fits within the area of the insulation layer 104. A bottom conductor layer 106 is deposited below and covers the entire area of the charge reservoir layer 105. This layer 106 can be patterned. It can be conductive over its entire area, or partially if coating has been applied. Carbon black is often chosen as the conductor layer because of its low cost and ease of deposition/printing. An electrolyte 107 permeates the structure. A laminate top cover J 08 acts as a top cover. Adhesive (109) must be present to hold 101 to 108.

This top cover creates problems, tt does increase the thickness of the display. A typical structure for printed electrochromic is 30 urn thick, with each laminate or substrate being 125 urn thick. Thin displays are needed for applications such as patches (an indicator for pharmaceutical drug dispensing), smart cards that must survive hot lamination during the manufacturing process where high pressure is applied and arty thickness variation is cause for breakage. Often, the substrate and top cover/laminate do not share the thermal expansion coefficient making the design prone to problem when exposed to wide ranges of environmental conditions, creating further problems during the manufacturing.

Accordingly, a display architecture that allows a single substrate is desired. Such a monolith structure is described in U.S. Patent No. 7,460,289 with a laminate structure as a top cover.

Some have suggested forming a solid electrolyte comprising a sheet of porous glass substrate impregnated with a solid, ion-conductive silver or alkali metal compound. One disadvantage of employing such an impregnated glass sheet is that, because it is a solid of limited flexibility, it would be difficult to assemble the component layers of an electrochromic device and achieve the intimate contact required between mis sheet and the adjacent layers. It does not solve the top cover problem and introduces, in fact, a slew of new problems for manufacturing.

Liquid electrolytes, because they are liquid, have the ability to intimately contact even irregularly shaped surfaces during the manufacturing process.

One potential way to prevent the electrolyte from leaving the display once built is to coat the structure with a polymer then dry it This has the disadvantage of introducing an additional printing step and a drying step, something that is not desired.

The aforementioned problems of prior art electrolytes are overcome by the self-sealing, polymer-functional liquid electrolyte of the present invention and its application. SUMMARY

The present invention provides for a display having a first side and a second side wherein the first side and second side are substantially parallel. The display includes: a single substrate, a self-sealing electrolyte layer, a coloring electrode, a second electrode and an insulator layer. The single substrate forms the first side of the display with the self-sealing electrolyte layer forming the second side of the display. The insulator layer is positioned between the coloring electrode and the second electrode. The coloring electrode, the second electrode, and the insulator layer are positioned between the first side and second side of the display. The self-sealing electrolyte contains a polymer and electrolyte and at least some portion of electrolyte from the self-seal ing electrolyte layer permeates throughout the layers of the display.

In one embodiment, the self-sealing electrolyte layer is touch-dry after the application of an elevated temperature during the formulation process.

In another embodiment, the self-sealing electrolyte is patterned forming non connected ionic paths where the non connected ionic paths are aligned perpendicularly to the coloring electrode and the second electrode. In one such embodiment, the non connected ionic paths can contain different electrolytes.

In still another embodiment, the second electrode includes an electrically conductive layer and a capacitive layer, and at least one of the electrically conductive layer and the capacitive layer correspond to a self-assembling layer. In one such embodiment, the self assembling layer is made from micron sized particles and/or nanometer sized particles, in another such embodiment, the self assembling layer is formed from carbon nanotubes, graphene, graphite, and carbon black. Fullerenes, copper, chromium, iron, lithium, nickel, silver, vanadium, zinc are also possible. In another such embodiment, the self assembling layer corresponds to the electrically conductive layer. In still yet another such embodiment, a first self assembling layer corresponds to the electrically conductive layer and a second self assembling layer corresponds to the conductive layer and the capacitive layer. The invention further provides for a self-sealing electrolyte for printed structures including a liquid electrolyte mixed with one or more polymer, monomer, oligomer, where the self sealing-electrolyte has a viscosity ranging from 10 mPas to 2000 Pas.

In one embodiment, the polymer mixture is heat polymerizable. In one such embodiment, (he polymer mixture is heat polymerizable at a temperature that is less than or equal to 150⁰C. In another such embodiment, the polymer mixture is radiation curable.

In one embodiment, the self-sealing electrolyte contains micron sized particles and/or nanometer sized particles, [n another embodiment, the self-sealing electrolyte contains carbon nanotubes, graphene, graphite, and carbon. In one embodiment, the self-sealing electrolyte contains oxygen scrubbers or scavengers.

The invention further provides for a method to manufacture a display containing a self- sealing electrolyte. The method includes the steps of: printing a first electrode layer onto a substrate; printing an insulator layer onto the first electrode layer; printing a second electrode layer onto the insulator layer; and printing a self-sealing electrolyte onto the second electrode layer to thereby form a self sealing electrolyte layer. The self sealing electrolyte includes an electrolyte and a monomer, an oligomer and/or a polymer.

In one embodiment, the method includes the step of applying heat and/or light to the self sealing electrolyte layer to thereby cure the self sealing electrolyte layer.

In another embodiment, the method includes the step of applying heat or light to the self sealing electrolyte layer to thereby generate a self assembling layer containing micron sized particles and/or nanometer sized particles. In one such embodiment, the self-assembling layer corresponds to an electrically conductive layer. In another such embodiment, the self- assembling layer corresponds to an electrically conductive layer and a conductive layer and a capacitive layer. In still yet another embodiment, the method includes (he step of applying to the self sealing electrolyte layer one or more of: heat; and light to thereby generate a self assembling layer containing the one or more of: carbon black, graphite, graphene, carbon nanotubes, fullerenes, copper, chromium, iron, lithium, nickel, silver, vanadium, and zinc. In one such embodiment, the self-assembling layer corresponds to an electrically conductive layer. In another such embodiment, the self-assembling layer corresponds to an electrically conductive layer and a conductive layer and a capacitive layer.

In another embodiment, the method includes the step of printing the self sealing electrolyte in a pattern to thereby form non connected ionic paths, where the non-connected ionic paths are aligned perpendicularly to the coloring electrode and the charge reservoir electrode.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are included to provide further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and, together with the description, serve to explain the principles of the disclosure.

In the drawings:

Figure 1 schematically represents an exemplary prior art system; Figure 2 schematically represents an exemplary system of the present invention; Figure 3 schematically represents an exemplary system of the present invention; Figure 4 schematically represents an exemplary system of the present invention;

Figure 5 schematically represents an exemplary system of the present invention; and Figure 6 schematically represents an exemplary system of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Reference will now be made in detail to Ae preferred embodiments of the present disclosure, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

The present invention is a monolithic architecture with no top cover mat relies on the electrolyte, in the self-sealing electrolyte, permeating a significant portion of the display, and the polymer, of the self-sealing electrolyte, to be self-sealing. In a preferred embodiment (referred to as COM on SUBSTRATE), each element of an eiectrochromic display is formed in a monolithic stack on a substrate. A conductive element is disposed on the substrate, followed by a capacitive layer, a separator layer, a conductive layer, and a segment layer having an adsorbed electrochromophore. A self-seating electrolyte permeates the monolithic stack, with the electrolyte allowing ionic conductivity between the capacitive layer and the segment layer and the polymer creating a sealing layer outside the segment layer. In another preferred embodiment (referred to as SEG on SUBSTRATE), each element of an electrochromic display is formed in a monolithic stack on a substrate. A segment layer having an adsorbed electrochromophore is disposed on the substrate, followed by a conductive layer (this order can be switched if the conductor is transparent enough), followed by a separator layer, by a capacitive layer, a second conductive layer, and a self-sealing electrolyte permeates the monolithic stack, with the electrolyte allowing ionic conductivity between the capacitive layer and the segment layer and the polymer creating a sealing layer outside the second conductive layer.

In the two previous embodiments, the self-sealing electrolyte is the last element of the display being printed and is applied on the side of display opposite the substrate side. The self-sealing electrolyte is introduced in the form of a mixture comprising a liquid compound that forms a solid polymer when exposed to thermal radiation and an ionic compound that is miscible with the first component. The solid polymer is isotropic. The mixture of the above components is prepared and introduced to the device before the polymerization is complete and while the mixture is still liquid. The electrolyte part of the mixture will permeate through mosl of the structure of the display. To foster bistability in the electrochromic display, the electrolyte should be electrically isolative, mat is containing no electron shuttles. The device is men heated to initiate and complete the polymerization reaction, to form a solid film on the outside of the display. This solid film is typically insulative.

The self-sealing electrolyte of the present invention differs from prior art self-sealing electrolyte such as that described in U.S. Patent No. 5,209,871. This patent describes a combination of two materials that are in liquid phase which forms a single gel after polymerization. It can be used in sandwich architectures. This is in contrast to the present invention where part of the electrolyte, from the self-sealing electrolyte, percolates/permeates through the porous structures in the display and another part of the self-sealing electrolyte creates a touch dry gel as described below. In a further embodiment, the self sealing electrolyte is introduced in the form of a mixture comprising a liquid compound (hat forms a solid polymer when exposed to thermal radiation, an ionic compound that is soluble with the first component. The solid polymer is isotropic. The mixture of the above components is prepared and introduced to the device before the polymerization is complete and while the mixture is still liquid. The device assembly is completed while the mixture is still liquid and the device is men exposed to light to initiate and complete the polymerization reaction, to form a solid electrolyte solution. This type of self- sealing electrolyte has the advantage to create a touch-dry coating. It allows roll to roll manufacturing of displays, as the back of a display printed on a web will not stain the front another display when the web is wound and unwound.

One way to achieve this self-sealing electrolyte is to mix a monomer, an oligomer, or polymer with the ionic liquid in a manner that generates a homogeneous mixture. This homogeneity is required to ensure the proper deposition. A preferred embodiment is PVDF. Other potential polymer/monomer/oligomer can be chosen from one or more of the following. polyvinyl idene fluoride, Kynar - co-polymer blend, plastic powders/fibers such as epoxy,

Polyester, LDPE; HDPE, PVOH, PF, PET, PEN, PBT, PTFE, Nylon, polypropylene, polyolefin, vinyl, polyamide, EVA, PU, Polystyrene, aery late, PVC Alkyd, Aery late, polymer polymethyl methacrylate.

At room temperature, The PDVF is typically not miscible in the ionic liquid, rather creating a suspension. Moreover, the PVDF is not transparent and has a milky look and feel. The mixture is heated above 70⁰C. At that temperature, the PVDF homogenizes in the IL, its viscosity increases and it becomes transparent. When brought back to room temperature, the PVDF and IL are now mixed properly and can be used as a self-sealing electrolyte.

Preferred monomers/polymers include, but are not restricted to methylmethacrylate, tert- butyl methacrylate, p-tert-butoxystryrene, acrylonitπle, ethylene oxide and vinylacetate.

Preferable ionic liquids include, but are not limited to Ethanolammonium formate, 1 -Ethyl-3- methyl-imidazolium dicyanamtde, l-Ethyl-3-methyl-imidazolium methanesulfonate, l-Ethyi-3- methyl-imidazolium nitrate, l-Ethyl-3-methyl-imidazolium tetrafluoroborate, l-Ethyl-3-methyl- imidazolium ethylsulfate, l -Butyl-3-methyl-imidazolium bromide, Ethylammonium nitrate, Trihexyltetradecylphosphonium decanoate, and Triisobutylmethylphosphonium tosylate. Further ionic liquids suitable for these embodiments include Butylmethylpyrrolidinium bis (trifluoromethylsu}fonyl)irnide, l-Ethyl-3-methylimidazolium chloride, l-Ethyl-3- methylimidazolium trifuoromethanesuifonate, l-Butyl-3-methylimidazoliurn trifluoromethanesulfonate, I -Ethyl-3-methylimidazolium chloride, l -EthyI-3- methylimidazolium chloride, l-Ethyl-3-methylimidazolium bromide, l-Butyl-3- methy I imidazolium chloride, l-Bυtyl-3-methylimidazolium bromide, l-Hexyl-3- methylimidazolium chloride, l-Hexyl-3-methylimidazolium bromide, l-Methyl-3- octylimidazolium chloride, l-Methyl-3-octylimidazolium bromide, l-Propyl-3- methylimidazolium iodide, l-Butyl-2,3-dimethylimidazolium chloride, l-Ethyl-3- methylimidazolium tetrafluoroborate. l-Ethyl-3-methylimidazolium hexafluorophospate, 1- Ethyl-3-methylimidazolium dicyanamide, l-Ethyl-3-methylimidazolium trifuoromethanesuifonate, l-Ethyl-3-methylimidazolium methanesulfonate, l-Butyl-3- methylimidazoli urn tetrafluoroborate, 1 -Bury 1-3-methy {imidazolium hexafluorophosphate, 1- Butyl-3-methylimidazolium hexafluorophosphate, l -Butyl-3-methyljmidazolium trifluoromethanesulfonate, l-Butyl-3-methylimidazolium methanesulfonate, I -Hexyl-3- methylimidazolium tetrafluoroborate, l-Hexyl-3-methylimidazolium hexafluorophosphate, 1- Methyl-3-octylimidazolium tetrafluoroborate, l-Methyl-3-octylimidazolium hexafluorophosphate, l-Butyl-2,3-dimethy}imidazolium tetrafluoroborate, 1 -Buty 1-2,3- dimethylimidazoiium hexafluorophosphate, Cyclohexyhrimethylammonium bi^trifluormemylsulfonyl)imide, bis(trifluoromethylsulfonyl)imide, ECOENG™ 418, (2- Hydroxyethyl)trimethylammonium dimethy (phosphate, l-Ethyl-3-methylimidazolium tosylate, ECOENG^¹ 41M, ECOENCf™ 21M, l-Butyl-4-methylpyridinium bromide, l-Butyl-3- methylpyridinium bromide, 1 -Buty l-3-methylpyridinium tetrafluoroborate, l-Butyl-4- methylpyridinium tetrafluoroborate, l-Butyl-4-methylpyridinium hexafluorophosphate, 1-Butyl- 3-methylpyridinium hexafluorophosphate, l-Ethyl-3-hydroxymethylpyridinium ethylsulfate, 1- Ethyl-3-methylpyridinium ethylsulfate, 3-Ethyl-3-methylpyridinium nonaflate, l-Butyl-3- methylpyridinium dicyanamide, l-Metyl-3-octylpyridintum tetrafluoroborate, Triethylsulfonium bis(triflouromethylsulfonyl)imide, Buty lmethy lpy rrol idinium bis(trifluoromethylsulfonyl)imide, ECOENG™ 41 1 , ECOENG™ 212, and ECOENG™. Preferable ionic solids include, but are not restricted to lithium perchlorate, lithium chloride, sodium chloride, lithium nitrate, sodium nitrate, lithium bromide, sodium bromide, potassium chloride, potassium bromide, lithium bistrifluorosulfonimide, lithium trifluoromethanesulfonate, lithium tetrafluoroborate, letramethylarnrnomum tetrafluoroborate and lithium hexafluorophosphate. These types of material allow a drying temperature in the range of 80⁰C to 150⁰C.

Another set of embodiments demonstrates the extensive control that can be achieved by integrating different liquids and solids into a self sealing electrolyte. Improved conductivity, reduced cost by allowance for impurity and limited color are possible. Selection of the elements added to the self sealing electrolyte improves the mechanical strength of the display by binding with particles and film throughout the display. MSQ can be used to improve the thermal performance of the self sealing electrolyte. The absence of an oxygen barrier on one side of the display can be compensated through the introduction of oxygen or water scavengers. Possible oxygen scavengers are PVDC, PVOH, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), Fe, tannin, DEHA Carbohydrazide, alkyd, deoxycholate, hydrazine, sulfites, potassium sulfites, hydroquinones, substituted hydroquinones, semi-hydroquinones, catechol, substituted catechols, carotenoids, flavonoids, cinnamic acids, benzoic acids, folic acid, ascorbic acid, tocopherols and tocotrienols, hydrazine and sulfites, Sodium and potassium sulfites tetrakis (hydroxy methyl), phosphonium chloride, erythorbic acid, ascorbic acid, hydroxylamine compounds, carbohydrazides and methyl ethyl ketoxime, linseed oil. Nothing precludes the addition of an additional laminate to improve performance. This configuration is particularly appealing for food packaging application where materials such as say Cryovac OS2000 film is already used.

In an alternative embodiment, the self sealing electrolyte is patterned to provide better performance and reducing ionic crosstalk between neighboring segments. This embodiment provides a new functional dimension to electrolytes through patterning. This patterning of the self sealing electrolyte allows the use of different electrolytes for different sections of the displays as well. For instance, one section of the display would be permeated by an electrolyte with perfect insolation, whereas another section would be permeated with an electrolyte that has a limited amount of electrically conductive species (e.g. ferrocene). The first section would display a high bistability. The second section a smaller bistability. Another advantage of patterning is that different electrolytes can be applied to different pan of the display. When different electrolytes are applied to optimize interaction with different materials, mostly notably (be chromogens increasing the design potential.

Patterning the self sealing electrolyte between die coloring and the charge reservoir electrodes allows the creation of de-facto anisotropy (albeit at a macro-level). Having a perfectly anisotropic electrolyte such as described in U.S. Patent No. 7,403,319 reduces cross talk and helps with lateral charge equilibrium in the display.

Another embodiment shows the greatly simplified manufacturing process using this self- sealing electrolyte. The use of a single substrate enables roll-to-roll (or web) manufacturing. There is a reduced need for alignment The self sealing electrolyte can be deposited using a wide range of equipment. This includes screen printing, flexography, gravure, lithography, inkjet, painting, spraying, aerosol, or combinations thereof. The viscosity of these inks, containing the self sealing electrolyte, can vary from 10 milli Pas for inkjet applications to up 2000 Pas for flexography applications. It can be self-sealed using a wide range of method, from heat curing, heat drying, UV curing, IR curing, induction heating, electric heating, microwave heating. UV curing can be facilitated through the addition of specific compounds, such as say polydimethylsiloxane.

In another embodiment, the self sealing electrolyte contains electrically conducting particles, preferably larger in size than the pores of the last layer printed prior to the electrolyte, in addition to the material that forms the top sealant layer. These particles form a self-assembling layer, which may be porous, between the previous printed layers and the top coat formed by the self-sealing electrolyte. These particles can be nanometer wide and up to a few micrometers wide. The can be, among others, carbon black, graphite, graphene, carbon nanotubes, fullerenes, copper, chromium, iron, lithium, nickel, silver, vanadium, zinc. This conducting layer is formed by the selective filtration of the conducting particles by the underlying layer, while the electrolyte percolates the material below. The resulting conductive layer improves charge distribution in the device by providing a lateral conductor. When applied to the SEG on SUBSTRATE type of architecture, this technique has the advantage of reducing the number of printing steps (and associated steps) by 1 (and associated one). In this embodiment, the printing steps now become: First a segment layer having an adsorbed electrochromophore is disposed on the substrate, followed by a conductive layer (this order can be switched if the conductor is transparent enough) to form a coloring electrode, followed by a separator layer, by a capaciti ve/charge reservoir layer, and finally a self-sealing electrolyte with particles. The components of the self sealing electrolyte permeate the monolithic stack, allowing ionic conductivity between the capacitive layer and the segment layer, creating a layer of conductor behind the capacitive layer, and the self sealing electrolyte also creates a sealing layer outside this conductive layer.

In a further embodiment, the self sealing electrolyte contains both electrically conducting and capacitive particles, preferably larger in size than the pores of the previously printed layer, in addition to the material that forms the top sealant layer. These particles can be nanometer wide and up to a few micrometers wide. The can be, among others, carbon black, graphite, graphene, carbon nanotubes. After printing, theses electrically conducting and capacitive particles form a continuous, self-assembling layer, which may be porous, between the previously printed layers and the topcoat. All of the porous layers below the topcoat are permeated by the electrolyte. This self assembling layer combines the functions of a charge reservoir/capacitive ("COM") layer and a lateral conductor layer. In this embodiment, the printing steps now become: First a segment layer having an adsorbed electrochromophore is disposed on the substrate, followed by a conductive layer (this order can be switched if the conductor is transparent enough) to form a coloring electrode, followed by a separator layer, and finally a self-sealing electrolyte with the electrically conducting and capacitive particles. The components of the self sealing electrolyte form different layers and perform several functions: forms capacitive layer behind the separator and permeate the monolithic stack and to allow ionic conductivity between this formed capacitive layer and the segment layer: creates a layer of conductor behind the capacitive layer; and also creates a sealing layer outside this conductive layer.

A traditional single substrate printed electrochromic structure (often referred to as monolith architecture) is based on an electrochromic display structure 100 as illustrated in Figure 1. This monolith electrochromic display structure 100 is viewed from the top of the display through the top substrate 101. This substrate 101 includes flexible material such as PET, PETG, PEN, thin glass, bendable glass, or any other transparent material. On this substrate 101, a transparent conductor material (metal, organic, semiconductor) layer 102 is deposited on part of the inside of the display. The deposition may be performed using a multiple of means such as printing, sputtering, ion beam deposition. On the bottom interface of layer 102, a layer 103 of electrochfomic material is deposited The layer 103 can be patterned or unpattemed. The areas($) of electrochromic malerial function as one or more electrodes ("SECi") or generally associated with the anode side. The area for such an electrode corresponds to active color area of the color changing structure. In one embodiment, the layer 103 of the one or more electrodes 103 will be totally covered by the area of the transparent conductor 102 layer. 1 n another embodiment the layer 103 of the one or more electrodes is built using a material with good lateral conductivity wherein the layer 103 may be incompletely covered by the area of the transparent conductor 102 layer. An insulation layer 104 is placed next to layer 103 covering its entire area of to insulate the SEG electrodes from the charge reservoir layer 105 ("COM") or generally associated with the cathode side. Layer 104 is an ion conductive insulating layer. The area of the charge reservoir layer 105 fits within the area of the insulation layer 104. A bottom conductor layer 106 is deposited below and covers the entire area of the charge reservoir layer 105. This layer 106 can be patterned. An electrolyte 107 permeates the structure. A laminate 108 acts as a top cover. Adhesive (109) must be present to hold 101 to 108. Figure 2 illustrates a monolith that uses a self-sealing electrolyte. This monolith electrochromic display structure 200 is viewed from the top of the display through the top substrate 201. This substrate 201 includes flexible material such as PET, PETG, PEN, thin glass, bendable glass, or any other transparent material. On this substrate 201 , a transparent conductor material (metal, organic, semiconductor) layer 202 is deposited on part of the inside of the display. The deposition may be performed using a multiple of means such as printing, sputtering, ion beam deposition. On the bottom interface of layer 202, a layer 203 of electrochromic material is deposited The layer 203 can be patterned or unpattemed. The areas(s) of electrochromic material function as one or more coloring electrodes ("SEG") or generally associated with the anode side. The area for such an electrode corresponds to active color area of the color changing structure. An insulation layer 204 is placed next to layer 203 covering its entire area of to insulate the SEG electrodes from the charge reservoir layer 205 ("COM") or generally associated with the cathode side. Layer 204 is an ion conductive insulating layer. The area of the charge reservoir layer 205 fits within the area of the insulation layer 204. A bottom conductor layer 206 is deposited below and covers the entire area of the charge reservoir layer 205. The electrolyte 207 is deposited then and permeates part or whole of layers 203, 204, 205, 206 and creates after drying/annealing a thin hardened protective layer 208. Figure 3 illustrates a monolith that uses a self-sealing electrolyte where the substrate is on (he back side. This monolith electrochromic display structure 300 is viewed from the top of the display through substrate 301. The substrate 301 includes flexible material such as PET, PETG, PEN, thin glass, bendable glass, or any other transparent or non-transparent material. On this substrate, a bottom conductor layer 302 is deposited. On top that layer interface, a charge reservoir layer 303 is deposited to complete the COM electrode. An ion conductive insulating layer 304 is placed next to layer 303 covering its entire area of to insulate it electrically. A transparent conductor material (metal, organic, semiconductor) layer 306 is deposited on part of the inside of the display. The deposition may be performed using a multiple of means such as printing, sputtering, ion beam deposition. This deposition must allow electrolyte to go through it. This can readily be realized using a meshed screen with thick wires. The electrolyte 307 is deposited then and permeates part or whole of layers 303, 304, 305, 306 and creates after drying/annealing a thin hardened protective layer (308). This monolith electrochromic display structure 300 i& viewed from the top of the display through the hardened layer 308. Figure 4 illustrates the patterning of the self sealing electrolyte for additional functionality. The substrate 401 forms the basis of the structure. The first electrode 402 is being printed (it can be the Counter electrode or the Working electrode). The working electrode has a conductor layer and a coloring layer. The Counter Electrode has a capacitive layer and a conductor layer. Separator 404 is then applied, following by the complementing electrode 405. That is if 403 is a working electrode, 405 is a counter electrode. If 403 is a counter electrode, 405 is a working electrode. Self sealing electrolytes) are then applied to different patterns (406, 407, 408). 406 and 407 can be of one kind, 408 of another kind with different ionic conductivity. The electrolyte will then permeate the structure, creating different funnels 409, 410, 411 forcing ionic conductivity only in the vertical direction. The top part of the electrolyte patterns dry into protective layers 413, 412, 414.

Figure 5 illustrates a monolith that uses a self-sealing electrolyte containing conducting particles that form a self assembling conducting layer between the charge reservoir layer and the protective sealing layer. This monolith electrochromic display structure 500 is viewed from the top of the display through the top substrate 501. This substrate 501 includes flexible material such as PET, PETG, PEN, thin glass, bendable glass, or any other transparent material. On this substrate 501, a layer with electrochromic material 502 is deposited on part of the inside of the display. The layer S02 can be patterned or unpatterned. The areas(s) of electrochromic material function as one or more electrodes ("SEG") or generally associated with the anode side. The area for such an electrode corresponds to active color area of the color changing structure. On the bottom interface of layer 502, a layer 503 of conductive material is deposited. The layer 503 can be patterned or unpatterned. An insulation layer 504 is placed next to layer 503 covering its entire area of to insulate the SEG electrodes from the charge reservoir layer 505 ("COM" ) or generally associated with the cathode side. Layer 504 is an ion conductive insulating layer. The area of the charge reservoir layer 505 fits within the area of the insulation layer 504. The self sealing electrolyte 506 is deposited then and permeates part or whole of layers 502, 503, 504. It creates a self assembling conductive layer 507 that forms by filtration of the conducting particles by the charge reservoir layer 505 below and covers the entire area of the charge reservoir layer 505 and a thin hardened protective layer 508.

Figure 6 illustrates a monolith that uses a self-sealing electrolyte containing conducting particles that form a self assembling conducting layer between the charge reservoir layer and the protective sealing layer. This monolith electrochromic display structure 600 is viewed from the top of the display through the top substrate 501. This substrate 601 includes flexible material such as PET, PETG, PEN, thin glass, bendable glass, or any other transparent material. On this substrate 601 , a layer with electrochromic material 602 is deposited is deposited on part of the inside of the display. The layer 602 can be patterned or unpatterned The areas(s) of electrochromic material function as one or more electrodes ("SEG") or generally associated with the anode side. The area for such an electrode corresponds to active color area of the color changing structure. On the bottom interface of layer 602, a layer 603 of conductive material is deposited. The layer 603 can be patterned or unpatterned. An insulation layer 604 is placed next to layer 603 covering its entire area. The self sealing electrolyte 605 is deposited then and permeates part or whole of layers 602, 603, 604. It creates a self assembling charge reservoir/capacitive 606 that forms by filtration of the conducting particles by the insulation layer 505 below, a conductive layer 607 that forms by filtration of the conducting particles by the created charge reservoir/capacity layer 606 below and covers the entire area of the charge reservoir layer 606 and a thin hardened protective layer 608. The present disclosure may be embodied in other specific forms without departing from the spirit or essential attributes of the disclosure. Accordingly, reference should be made to the appended claims, rather than the foregoing specification, as indicating the scope of die disclosure. Although the foregoing description is directed to the embodiments of the disclosure, it is noted that other variations and modification will be apparent to those skilled in the art, and may be made without departing from the spirit or scope of the disclosure. From the perspective of device functionality, this includes and is not limited to photovoltaic systems, sensing systems, primary battery systems, and secondary battery systems.

Claims

What is claimed:

1. A display having a first side and a second side wherein the first side and second side are substantially parallel, said display comprising: a single substrate forming the first side of the display; a self-sealing electrolyte layer forming the second side of the display, said self-sealing electrolyte containing a polymer and electrolyte; a coloring electrode; a second electrode; and an insulator layer positioned between the coloring electrode and the second electrode; wherein the coloring electrode, the second electrode, and the insulator layer are positioned between the first side and second side of the display, and wherein at least some portion of electrolyte from the self-sealing electrolyte layer permeates throughout the layers of the display.

2. A display as in claim 1 , wherein the self-sealing electrolyte layer is touch-dry.

3. A display as in claim 1 , wherein the self-sealing electrolyte is patterned and comprises non-connected ionic paths, said non-connected ionic paths being aligned perpendicularly to the coloring electrode and the second electrode.

4. A display as in claim 3, wherein the non-connected ionic paths contain different electrolytes.

5. A display as in claim I, wherein the second electrode comprises an electrically conductive layer and a capacttive layer, and wherein at least one of the electrically conductive layer and the capacitive layer correspond to a self-assembling layer.

6. A display as in claim 5, wherein the self assembling layer is made from one or more of micron sized particles and nanometer sized particles.

7. A display as in any of claims 5 and 6, wherein the seif assembling layer is formed from one or more of: carbon black, graphite, graphene, carbon nanotυbes, fullerenes, copper, chromium, iron, lithium, nickel, silver, vanadium, and zinc.

8. A display as in any of claims 5, 6 and 7, wherein said self assembling layer corresponds to the electrically conductive layer.

9. A display as in any of claims 5, 6 and 7, wherein a first self assembling layer corresponds to the electrically conductive layer and a second self assembling layer corresponds to the conductive layer and the capacitive layer.

10. A seif-sealing electrolyte for printed structures comprising a liquid electrolyte mixed with one or more polymer, monomer, oligomer, said self sealing-electrolyte having a viscosity ranging from 10 mPas to 2000 Pas.

11. An electrolyte as in claim 10, wherein the polymer mixture is heat porymerizable.

12. An electrolyte as in claim 1 1 , wherein the polymer mixture is heat poh/merizable at a temperature that is less than or equal to 150⁰C.

13. An electrolyte as claim 12, wherein the polymer mixture is Radiation Curable.

14. An electrolyte as in any of claims 10, 1 1, 12, and 13, wherein the self-sealing electrolyte comprises one or more of micron sized particles and nanometer sized particles.

15. A self-sealing electrolyte as in any of claims 10, 11, 12, 13 and 14, wherein said self sealing electrolyte comprises one or more of: carbon black, graphite, graphene, carbon nanotubes, fuilerenes, copper, chromium, iron, lithium, nickel, silver, vanadium, and zinc.

16. A self-sealing electrolyte as in any of claims 10, 11, 12, 13, 14, and 15, further comprising oxygen scrubbers or scavengers.

17. A method comprising: printing a first electrode layer onto a substrate; printing an insulator layer onto said first electrode layer; printing a second electrode layer onto said insulator layer; and printing a self-sealing electrolyte onto said second electrode layer to thereby form a self sealing electrolyte layer, where said self sealing electrolyte comprises an electrolyte and one or more of the following: a monomer, an oligomer and a polymer.

18. The method of claim 17, further comprising the step of: applying to the self sealing electrolyte layer one or more of: heat; and light to thereby cure the self sealing electrolyte layer.

19. The method of claim 17, wherein said self-sealing electrolyte further comprises one or more of: micron sized particles; and nanometer sized particles.

20. The method of claim 19, wherein said self-sealing electrolyte further comprises one or more of: carbon black, graphite, graphene, carbon nanotubes, fullerenes, copper, chromium, iron, lithium, nickel, silver, vanadium, and zinc.

21. The method of claim 19, further comprising the step of: applying to the self sealing electrolyte layer one or more of: heat; and light, to thereby generate a self assembling layer containing the one or more of micron sized particles and nanometer sized particles.

22. The method of claim 20, further comprising the step of: applying to the self sealing electrolyte layer one or more of: heat; and light to thereby generate a self assembling layer containing the one or more of: carbon black, graphite, graphene, carbon nanotubes, fullerenes, copper, chromium, iron, lithium, nickel, silver, vanadium, and zinc.

23. The method of any of claims 21 and 22, wherein the self- assembling layer corresponds to an electrically conductive layer.

24. The method of any of claims 21 and 22, wherein the self-assembling layer corresponds to an electrically conductive layer and a conductive layer and a capacitive layer.

25. The method of any of claims 17 and 18, wherein the step of printing a self-seal ing electrolyte comprises: printing the self sealing electrolyte in a pattern to thereby form non-connected ionic paths, wherein the non-connected ionic paths are aligned perpendicularly to the coloring electrode and the second electrode.